No description available.

Swedes are extremely common as a root vegetable in Europe, USA, and Canada but are affected by the occasional presence of Brown Heart (BH) disorder affecting the marketable swede root. The incidence of BH has been reported worldwide however it is very difficult to breed resistance due to its sporadic occurrence with no external symptoms to select for. BH has been attributed to boron availability but attempts to link BH appearance definitively with boron deficiency have been difficult. Anecdotal evidence from breeders and growers highlighted the recent co-appearance of BH and frost injury in the field and it was postulated that if an association (physiological or genetic) can be determined between BH appearance and another more easily assessed trait such as frost susceptibility, then a frost tolerance screen may be developed as a useful surrogate method to screen for BH resistance. Frost hardiness assessment of 12 swede genotypes including some F1 hybrids was carried out. Results showed that some genotypes (like Ag31, Me77c and Or13) were more susceptible to frost (EL50 circa -7 ˚C) whilst others (like Gr19 and Ly01) were classified as more tolerant. Breeder trials data from the UK and Germany over a 10 year period showed that 85% of the BH incidence was associated with genotypes that had the frost susceptible lines Ag31, Or13 or Me77c in their parentage. To investigate this association further, frost susceptible and tolerant genotypes, together with a number of their F1 hybrids, were evaluated in a field trial for their response to boron treatments (0.00, 1.35, 1.80 and 2.70 kg B ha-1). At maturity, BH incidence and its severity was predominantly affected by genotype but could be ameliorated by boron application. Ag31 was confirmed to be the most susceptible to BH, and Or13 and Me77c were intermediate in their susceptibility. F1 hybrids between any two susceptible parents were also susceptible to BH. In contrast, genotypes Gr19 and Ly01 were confirmed to be highly resistant to BH and did not show any BH symptoms even at zero boron applied. F1 hybrids between resistant and susceptible lines demonstrated the BH resistant phenotype. Resistance to BH was therefore confirmed as a dominant trait with either a BHBH or BHbh genotype, whilst susceptibility was recessive bhbh. A degree of quantitative variation existed in the severity of the BH suggesting that BH resistance was not a single gene effect. BH severity was significantly negatively correlated (r = - 0.632) with root boron content in susceptible genotypes. The genotypes which were BH resistant in this trial were also more tolerant to frost in screening tests and this association was investigated further at a molecular level. Cold acclimation (CA) for 14 days at 4 ˚C positively affected the response of swede to frost, lowering the EL50 by -1.5˚C, and boron reduced the EL50 by -2.2˚C under non-acclimating conditions and by -1.2˚C under CA. Both boron and CA increased the catalase (CAT) and super oxidase dismutase (SOD) concentrations in swede leaves. Molecular analysis clearly demonstrated the presence of the B.napus cold response gene in swede, BN115, and was shown to be up-regulated due to both CA and boron application but differed between the two genotypes tested. The more frost resistant Gr19 showed a better response than the susceptible Ag31. Boron application reduced EL50 by -2.3˚C for Ag31 and -3.1˚C for Gr19. Given the association between frost tolerance and BH resistance it is suggested that a frost test screen could be used as a useful surrogate method to screen for BH resistance in swede breeding programmes.

Subduction zones, such as the Andean convergent margin, are the sites at which new continental crust is generated, and where subducting material is either recycled to the crust via arc magmatism or transferred to the deep mantle. The composition of arc magmas and associated new continental crust reflects variable contributions from mantle, crustal and subducted reservoirs. Insights into crustal growth and recycling processes in the southern Central Andes, specifically in the Pampean flat-slab segment, have been gained by utilising a range of petrological, geochronological and geochemical techniques. These techniques have been applied to a suite of Late Cretaceous (~73 Ma) to Late Miocene (~6 Ma) intrusive (granitoids) and extrusive (basalts to rhyolites) arc rocks collected from an east - west transect across the Andean Cordillera. The oxygen and hafnium isotopic composition of the accessory mineral zircon allows mantle-derived melts contaminated with older, upper continental crustal to be identified. Boron isotopic compositions of melt inclusions, combined with concentrations of certain incompatible trace elements, can be used to assess the source and influence of fluids derived from subducting material on the melt source region. The southern Central Andes provides a particularly interesting area to study these processes as the thickness of the continental crust has increased significantly over the course of the Cenozoic (from ~35 km to >50 km) and the angle of the subducting Nazca plate has shallowed since ~18 Ma, causing the position of the volcanic arc to migrate to the east. In order to unravel the complexities involved with constraining the contributions to arc magmas at an active continental margin, a range of geochronological, geochemical, and geothermobarometric techniques, including high resolution, micro-analysis of mineral phases and melt inclusions, have been applied. High resolution, U-Pb dating of magmatic zircon has improved regional stratigraphy in the Pampean flat-slab segment (between ~29 and 32 °S) and provided an accurate temporal constraint for geochemical and geothermobarometric data. The results of in-situ O and Lu-Hf isotope analysis of zircon show both distinct temporal and spatial variations across the Andean arc. The observed isotopic variability is attributed to variable contamination of mantle-derived melts with distinct Andean basement terranes, which vary east – west in composition and age. ‘Mantle-like’ δ18O(zircon) values, juvenile initial ƐHf(zircon) values and a lack of inherited, xenocrystic zircon cores, suggests the Late Cretaceous (~73 Ma) to Eocene (~39 Ma) plutons located in the Principal Cordillera of Chile, experienced very little interaction with the upper continental crust. Amphibole – plagioclase geothermobarometry indicates these calc-alkaline granitoids, which form extensive north – south trending belts, were emplaced at shallow depths in the crust (~4 – 5 km). Therefore the Late Cretaceous to Late Eocene is interpreted as a period of significant upper crustal growth. The isotopic variability in the Late Oligocene (~26 Ma) to Late Miocene (~6 Ma) arc magmatic rocks demonstrates that during thickening of the continental crust and migration of the Andean arc to the east, arc magmas assimilated Late Paleozoic to Early Mesozoic basement. In addition, arc magmas erupted/emplaced in the Argentinean Precordillera (i.e. farthest east from the trench) assimilated a Grenville-aged (~ 1330 – 1030 Ma) basement. The youngest arc magmas (~6 Ma) erupted in the Frontal Cordillera also show evidence for the assimilation of this ancient basement terrane, potentially signalling under-thrusting beneath the Frontal Cordillera. Overall, the later part of the Cenozoic represents a period of crustal reworking. Boron concentrations and isotope ratios measured in pyroxene hosted melt inclusions and for the first time in zircon hosted melt inclusions, are higher than the values expected for the mantle wedge and show significant variations with time. The source of the Paleocene (~61 Ma) arc magmas were influenced by fluids primarily derived from altered oceanic crust. Lower δ11B values and boron concentrations obtained for Oligocene (25 – 23 Ma) arc magmatic rocks reflects a diminished influence of slab-derived fluids reflecting a greater depth to the top of the slab. Fluids derived from serpentinite influenced the source of the arc magmas after ~19.5 Ma. This has been linked with the intersection of the Juan Fernández Ridge, a volcanic seamount chain associated with hydrated and serpentinised oceanic lithosphere.

The development of molybdenum - silicon - boron (Mo-Si-B) composites having a combination of high temperature strength, creep, and oxidation residence has the potential to substantially increase the efficiency of gas turbines. The refractory nature of the αMo, Mo3Si (A15), and Mo5SiB2 (T2) phases results in good strength and creep resistance up to 1300°C. At this temperature, the formation of a borosilicate surface scale from the two intermetallic phases is able to provide oxidation resistance. However, realization of these advantages has been prevented by both a high brittle to ductile transition temperature and difficulty in forming the initial surface borosilicate to provide bulk oxidation resistance. This dissertation addresses two factors pertaining to this material system: 1) improvements to powder processing techniques, and 2) development of compositions for oxidation resistance at 1300°C. The processing of Mo-Si-B composites is strongly tied to their mechanical properties by establishing the αMo matrix, limiting impurity content, and reducing silicon supersaturation. These microstructural aspects control the brittle to ductile transition temperature which has traditionally been too high for implementation of Mo-Si-B composites. The processing here built upon the previously developed powder processing with silicon and boron nitrides which allowed for a low oxygen content and sintering of fine starting powders. Adjustments were made to the firing cycle based upon dew point measurements made during the hydrogen de-oxidation stage. Under a relatively high gas flow rate, 90% of the total water generated occurred during a ramp of 2°C /min between 450 and 800°C followed by a hold of 30 minutes. The oxidation resistance of Mo-Si-B composites was studied for a wide range of compositions. Silicon to boron atomic ratios were varied from 1 to 5 and iron, nickel, cobalt, yttria, and manganese were included as minor additions. In all these compositions, the αMo volume fraction was kept over 50% to ensure the potential toughness of the composite. For the oxidized surface glass, a silica fraction of 80 to 85% was found to be necessary for the borosilicate to have a sufficiently high viscosity and low oxygen permeability for oxidation resistance at 1300°C. For the Mo-Si-B bulk composition this corresponds to a Si/B atomic ration of 2 to 2.5. Higher viscosity compositions failed due to spallation of poorly attached, high silica scales. Lower viscosity compositions failed from continuous oxidation, either through open channels or repetitive MoO3 bubble growth and popping. Additionally, around 1% manganese was necessary for initial spreading of the borosilicate at 1300°C. In conjunction with flowing air to prevent MoO3 accumulation, oxidation weight loss rates below 0.05 mg/cm2-hr were measured. Finally, a theory is proposed here to describe the mechanisms responsible for the development of oxidation resistance. This theory involves three stages associated with: 1) generation of an initial surface borosilicate, 2) thickening of the borosilicate layer, and 3) slow parabolic oxidation controlled by the high silica surface scale.

Several electrochemical processes are modeled at process levels and atomic scales. Processes are presented for acid generation and ion exchange media regeneration, along with corresponding process models. Transport and reaction processes in individual ion exchange beads are also modeled. Acids of mild strength (pH = ~1-2) are generated from electrolyte solutions and their strength is effectively modeled as a function of time. The regeneration of ion exchange media is also modeled, to close agreement with measurements, and the process model is reconciled with a model for solute flux from an individual ion exchange bead. Together, the models show that the "gentle" regeneration process is controlled by the plating rate. Processes interior to the particle are controlled by diffusion, but all processes are faster than the characteristic time for plating. In a separate process, an electrochemical method is used to produce hypochlorite for disinfection. The process generates perchlorate as a toxic byproduct. Density function theory is used to construct an atomic-scale model of the mechanism for producing perchlorate, as well as the aging of the boron-doped diamond anode used in the process. The mechanism shows that the boron-doped diamond surface plays an important role in chemisorbing and stabilizing radicals of oxychlorine anions, allowing the radicals to live long enough to react and form higher ions like perchlorate. Wear mechanisms that occur on the anode are shown to oxidize and etch the surface, changing its chemical functionality over time. As the surface ages, the overpotential for water oxidation is decreased, decreasing the efficiency of the electrode.

No description available.

No description available.

The topological diversity of lithium-boron imidazolates LiB(imid)4 was studied by combining topological enumeration and ab initio DFT calculations. The structures based on zeolitic rho, gme and fau nets are shown to be stable and have high total hydrogen uptake (6.9–7.8 wt.%) comparable with that of MOF-177. / Dieser Beitrag ist mit Zustimmung des Rechteinhabers aufgrund einer (DFG-geförderten) Allianz- bzw. Nationallizenz frei zugänglich.

This thesis describes investigations into the utility of boron fluorides and tetrafluoroborates as sources of nucleophilic fluorine. Chapter 1 discusses the history and importance of the field of organofluorine chemistry and outlines some of the principle motivations for the site-selective fluorination of organic molecules. Some of the most commonly useed methods of nucleophilic fluorination are briefly surveyed, with an emphasis on the formation of fluorinated stereogenic centres. Literature precedent for the use of tetrafluoroborates and boron trifluoride as nucleophilic fluorinating agents is also presented. Chapter 2 describes the development of a highly regio- and stereoselective S_Ni-type ring-opening fluorination of trans-β-substituted aryl epoxides using BF₃●OEt₂ as a nucleophilic fluorinating agent. This robust and scalable protocol grants efficient access to a variety of functionalised benzylic fluoride building blocks, and provides a solution to the problem of stereocontrol in the synthesis of this class of compounds. To highlight the utility of the resultant syn-fluorohydrins in the synthesis of stereodefined β-fluoro β-aryl amines, their elaboration to a range of aryl-substituted β-fluoroamphetamines is demonstrated. Chapter 3 introduces the concept of tuning the reactivity of BF₃ by replacing one or two of the fluoro ligands on boron for electron-donating alkoxy group(s). On this basis, pinacolatoboron fluoride (pinBF) [which may be prepared in situ by pre-mixing BF₃●OEt₂ and bis(O-trimethylsilyl)pinacol] is identified as a superior reagent to BF₃●OEt₂ for the ring-opening fluorination of trans-β-substituted aryl epoxides bearing electron-rich aryl groups. Chapter 4 details a highly regioselective and stereospecific S_N2-type ring-opening fluorination of 2,3- and 3,4-epoxy amines using HBF₄●OEt₂ as a nucleophilic flurine source. The reactions are both operationally simple to perform and readily scalable, and proceed to completion within 5 min at ambient temperature, providing a highly practical and economical route to stereodefined amino fluorohydrins. To highlight the synthetic utility of this reaction in the preparation of pharmaceutically-important β-fluoro amines, a concise de novo asymmetric synthesis of (S,S)-3-deoxy-3-fluorosafingol is performed. Chapter 5 chronicles the successful development of a protocol for the direct hydroxyfluorination of allylic amines to the corresponding amino fluorohydrins, using m--CPBA as the oxidant and HBF₄●OEt₂ in a dual role as both the Brønstead acid N-protecting agent and nucleophilic fluorine source. With chiral allylic amines which are conformationally biased or constrained, the diastereofacial selectivity of the reaction can be controlled by altering the concentration of HBF₄●OEt₂ employed in the reaction, allowing for a diastereodivergent hydroxyfluorination process. The synthetic utility of this methodology is demonstrated via its application to the diastereodivergent synthesis of 4-deoxy-4-fluoro-L-xylo-phytosphingosine and 4-deoxy-4-fluoro-L-lyxo-phytosphingosine, each in 5 steps from Garner's aldehyde. Chapter 6 contains full experimental procedures and characterisation data for all compounds synthesised in chapters 2, 3, 4 and 5.

The experimental work discussed in this thesis explores the effects of metal modification on the electroanalytical ability of boron doped diamond electrodes. Boron doped diamond (BDD) electrodes have found increased application to electroanalysis in the past two decades, yet relatively little of the literature is focused on metal, nano and microparticle modification of the substrate. In this thesis three metals have been used to modify the BDD electrode; bismuth, antimony and nickel. Bismuth and antimony nanoparticle modified BDD electrodes were directly compared to unmodified BDD and a bulk bismuth electrodes in the determination of trace levels of cadmium and lead using anodic stripping voltammetry. In both instances, the modified electrode allowed for the simultaneous determination of each analyte that was otherwise unattainable at the unmodified BDD electrode. The nickel modified BDD (Ni-BDD) electrode was used in the determination of organic analytes, namely glucose, methanol, ethanol and glycerol. The nickel nano and microparticle electrodes gave the characteristic Ni(OH)₂/NiOOH redox couple in alkali pH, the oxidised form of which (NiOOH) catalysed the oxidation of the organic analytes. The chapter on glucose sensing with the Ni-BDD electrode is preceded by an extensive literature review on the advances of non-enzymatic glucose sensing, and the application of catalytic metals and nanomaterials in this field. Throughout the course of this DPhil, there has been a collaborative project between Asylum Research and myself within the Compton group to develop a commercial electrochemical atomic force microscope (EC-AFM) cell. The aim was to produce an adaptable EC-AFM cell capable of dynamic electrochemical experiments whilst simultaneously or instantaneously acquiring an AFM image of the modified surface, in-situ. This project was successful, and the EC-AFM cell has contributed to a number of chapters in this thesis, and has now been commercialised.